Composition comprising aqueous dispersion of aminoplast condensate and an oxetane



United States Patent Office Bfiidflh Patented dart. 22, E333 Philadelphia, Pa, as-

Philadelphia, Pa,

This invention relates to compositions for the treatment of textile materials, and it is particularly concerned with the treatment of textile materials of wool and cellulosic type to improve their characteristics, especially to render the fabrics resistant to crushing and to shrinkage on laundering. It is also concerned with the treated fabrics thereby obtained and with methods for treating fabrics with the novel compositions. This application is a continuation-in-part of our copending application Serial No. 792,991, filed February 13, 1959, now abandoned.

Heretofore, condensates of formaldehyde with melamine, urea and their derivatives including cyclic urea derivatives, such as N,N-ethyleneurea and methylol melamines and ureas and their alkylated derivatives and also N,N-trimethyleucurea, have been applied to Wool and cellulosic fabrics, such as cotton, for the purpose of imparting crush-resistance and reduced shrinkage on laundering. However, fabrics treated with these condensates pick up chlorine during bleaching operations using chlorine,

such as those using it in the form of a hypochlorite. On

ironing the fabrics that have been bleached in this manner, severe discoloration and/or loss in tensile and/or tear strengths have generally resulted. In those cases where severe discoloration is encountered, the treatment with these condensates is unsuitable, especially when a White fabric is desired. In some cases, as much as 90% loss in strength is encountered as a result of the action of heat, as in ironing, on fabrics treated with these condensates and bleached with chlorine. The presence on a fabric of a thermoset condensate of formaldehyde with melamine frequently gives rise to some discoloration of the fabric on the mere treatment with a hypochlorite bleach unless care is taken to avoid excess chlorine and elevated temperatures. Ironing in such cases serves to aggravate the discoloration.

The Suen patent, No. 2,730,427, discloses the treatment of textile materials for imparting resistance to shrinkage and creasing with certain diglycidyl ethers having the Formula I:

wherein R is an alkylene group of from 2 to 6 carbon atoms. United States Patent 2,752,269 discloses the use of other types of glycidyl polymers and condensates such as those obtained by condensation of glycerol and epichlo- .rohydrin and polymers of allyl glycidyl ether. The use of the glycidyl compounds of these patents, however, is quite expensive and comparatively iueffrcient with respect to certain nitrogen-containing condensates, and especially those of formaldehyde with N,N-ethyleneurea and melamine. It is generally required that about three times as much of one of these glycidyl compounds must be applied to a cotton fabric to obtain crush-proofing action comparable to that obtained with a given amount of the nitrogen-containing aminoplasts just mentioned. Generally, also the diethers are two or three times as expensive as these aminoplasts and as much as fifteen times the cost of the simpler urea-formaldehyde condensate.

U.S. Patent 2,794,754 discloses the use of a mixture of an aminoplast condensate with a compound containing a plurality of Vic-epoxy groups. The compounds of this patent, however, are comparatively inefficient in protecting the fabric from chlorine damage by certain nitrogencontaining condensates, and especially those of formaldehyde with N,N'-ethyleneurea and melamine, when used in admixture therewith. In addition, the Vic-epoxy compounds tend to pick up iron in hard water and thereby produce a discoloration on washing of the fabric which cannot be removed by normal bleaching operations.

it has been found in accordance with the invention that the incorporation of a minor proportion of certain watersoluble or easily water-dispersible oxetanes in aqueous solutions of water-soluble aminoplast condensates selected from the group consisting of condensates of formaldehyde with aminotriazines, certain triazones, N,N'-trimethyleneurea, and N,N-ethyleneurea, and their alkylated erivatives serves to eliminate, or reduce to within prac tical limits, the chlorine damage that would otherwise occur as a result of the treatment with such aminoplasts. Surprisingly, the improvement is accomplished without the necessity to apply excessive quantities of the shrinkproofing or crease-proofing composition in spite of the fact that the oxetanes are incapable of crease-proofing cellulosic fabrics when applied without an aminoplast under conditions similar to those under which the mixture is applied. The oxetanes of the present invention are from live to ten times as efficient as the Vic-epoxy compounds of the U.S. patent 2,794,754 in reducing chlorine damage bydiscoloration and degradation caused by the aminoplast condensates and have little or no tendency to pick up iron from hard waters as the Vic-epoxy compounds do.

For convenience of reference hereinafter, the aminopla st is referred to as component A and constitutes the major or predominant part of the shrink-proofing, creaseprooting or crush-proofing components of the composition. The oxetane component is hereinafter referred to as component B and constitutes from about 5% to about 40% by weight of the effective components, that is the total Weight of the aminoplast and oxetane components. For most purpoess, from the standpoint of cost, efi'iciency, optimum freedom from discoloration, and minimum tensile loss on ironing or heating after chlorination, it is preferred to use from 5% to 20% by weight of component B and 95% to by weight, respectively, of compovnent A.

In accordance with the present invention, the aminoplast compositions with which the invention is concerned are water-soluble in character and include the simple condensates of N,N'-ethyleneurea, certain triazones described hereinafter and aminotriaziues, such as melamine or its derivatives including N-(Q-Cflalkylmelamines, N,N-di(C -C.,) alkylmelamines, and N,N-di(C -C alkylmelamines, with formaldehyde as well as the alkylated methylol derivates thereof, in which the alkylation is effected with lower alcohols from 1 to 3 carbons or with small proportions of higher alcohols, such as the butyl alcohols or with mixtures of such higher alcohols with the lower alcohols, so that in any event the alkylated methylol derivatives are water-soluble or self-dispersible readily in water. Any water-soluble condensate of formaldehyde with melamine, N,N'-ethyleneurea, or N,N'- trimethyleneurea may be employed. Examples of specific compounds that may be used include trimethylolrnelarninc, dimethylol-N,N-ethyleneurea, and dimethylol-N,N-tri- *methyleneurea. The triazones that may be used include the polymethylol tetrahydro-s-triazones substituted in the epmeee 3 S-position by an alkyl or hydroxyalk-yl group. These triazones have the Formula II:

HOCHz-N N-C-HZOH H2O Ha (II) R where R is selected from the group consisting of Z-hydroxyethyl, Z-hydroxypropyl, and alkyl groups having 1 to 4 carbon atoms. In addition, the alkylated derivatives of these polymethylol condensates obtained from the lower alcohols from methyl through butyl may be employed. Examples include dimethoxymethyl-N,N'-di methylmelamine, dimethoxymethyl N,N' ethyleneurea, dimethoxymethyl 5- (fi-hydroxymethyl)tetrahydro-s-triazone-2, and so on. Again, it should be noted that the condensates, employed as component A may be fairly sharply defined compounds including those just named as well asothers, or it may comprise mixtures of compounds of varying degrees of substitution wherein the number of methylolgroups or alkoxymethyl groups may be different in the several compounds Within the mixture. For the most efficient action, the aminoplasts derived-from N,N- ethyleneurea and from melamine are preferred.

Component B may consist of any oxetane within the scope of Formula III following:

in which R is selected from the group consisting of H, -CH (C H OH, -CH Cl, and alkyl groups having 1 to 8 carbon atoms, 11 is an integer having a value of 2 to 3, and x is an integer having a value of 1 to 1-1, preferably 1 to 3.

The aqueous solution of the water-dispersible condensates, including component A and component B, may contain such condensates in-a concentration in about 2% to 25% or more, based on total condensate solids. The particular concentration applied in any given instance may depend on the purpose for which the condensate mixture is applied and on the particular substrate or fabric to whichit is applied. In the case of. cotton, the concentration is preferably from 2% to 12%, whereas in application to rayon the concentration is preferably 5% to 20%, when the purpose of the application is to impart creaseresistance, crush-resistance,. or shrinkage stabilization. In-the case of wool, the concentration is preferably from 5% to 15%. While it is generally unnecessary, component A and-component B may be reacted together provided any such reaction leaves the finalcondensate in'a water-soluble condition. However, for most purposes, it is preferred not to co-react these components.

The solution containing the mixture of' condensates (component A and component B), or the co-reacted' condensates is stable when subjected to-ordinary conditions of storage and can be sold, shipped and stored assuch. Shortly before use, an' acidic catalyst may be added, if desired, as pointed out hereinafter.

An acidic catalyst for catalyzing thecondensation of the. aminoplast and the reaction of the cellulose with the oxetane and the aminoplast israpplied to the. fabric either simultaneously with the condensates or before or after the mixture of condensates is applied. Preferably the acidic catalyst is dissolved in the aqueous solution-of the mixture of condensates. Suitable catalysts include ammoniumphosphate, ammonium fluoborate, ammonium thiocyanate, hydrochloric or other acid salts of a hydroxy aliphatic amine including 2-methyl-2-amino-l-propan0l, 2"- methyl-Z-amino 1,3-propandiol,, tris-.(hydroxymethyl)- aminomethane, Z-phenyl-iZ-amino 1-propanol, Z-methyl-Z- amino-l-pentanol, Z-aminobutanol, triethanolamine, 2-

amino-Z-ethyl-l-butanol, and also ammonium chloride, pyridine hydyrochloride, aluminum chloride, benzyldimethylammonium oxalate, magnesium perchlorate, zinc silicofluoride, zinc perchlorate, magnesium thiocyanate, zinc thiocyanate, zinc fluoborate, zinc nitrate, boron fluoride, and especially the boron fluoride ether complex of the boron fluoride water complex, hydrogen fluoride, hydrochloric acid, ammonium chloride, ammonium acid fluoride, phosphoric acid, oxalic acid, tartaric acid, citric acid, sulfuric acid and sodium bisulfate. The preferred catalysts which seem to be outstanding in their efficiency of action and freedom from detrimental effect on fabrics, especially with cellulosic types of fabrics, are the zinc salts such as zinc fluoborate and zinc nitrate. The catalyst is generally introduced into the aqueous solution of the condensates at a concentration of about 0.1 to 2% and preferably approximately 1%. The catalyst may be present in an amount from about /2 to about 25% on the weight of condensate solids (including the aminoplast and oxetane).

The compositionsof the present invention may be applied to fibers, filaments, yarns, or. fabrics of wool or cellulosic type and especially those of cotton or rayon for various purposes; For example, they may be applied simply tomodify the feel or texture of. the surface of the fabrics. When applied in greater quantities,- the condensates of the present invention may be used to make the fabrics wrinkle-resistant, crush-resistant and crease resistant; The application of increasing amounts of the condensates serves to provide proportionately increased reduction in shrinkage of the treated fabric on laundering, and when about 3% to 7% by Weight of the'condensate', based on the weight of the fabric, is applied, the wool or cellulosic fabric is generally substantially stabilized against shrinkage on laundering. The application of the condensates of the present invention may be employed for the purpose of aiding embossing operations. They also may be applied to fabrics as partof a process for their conversion to pliss fabrics and embossed fabrics;

The aqueous solution of the condensates may be applied by spraying, brushing, dipping, as-in padding, orby rollercoating. After the application, excess-may be removed, as by squeezing or squeegeeing. The treated fabric is then dried, such as by air-drying at room temperature or by the treatment with" heated air under conventional conditions.

After the fabric has been dried, the condensate mixture is baked or cured on the fabric at a temperature of about 220 to 450 F. or higher, depending'on the particular substrate. The time may be varied generallyin inverse proportions to the temperature; For example, the time may vary from about five seconds to half an hour. A time of 30 seconds at 400 F. is quite practical and a time of 15 to 30. minutes at 220 F. is generally satisfactory. The baking operation may simply be a con tinuation of the drying operation so that drying and curing may be effected in essentially a one-stage procedure.

The drying and/or the baking maybe effected by any suitable means for applying the heat, such as by the application of heated air currents, by infra-red radiation or by high frequency electric induction.

The oxetanes of Formula III are either known com pounds or homologs of known compounds made in the same way as'the latter but with homologousstarting materials. Examples of preparation of the compounds in which parts and percentages are by Weight unless otherwise indicated are as-follows:

EXAMPLE A Preparation of 3-Ethyl-3-Hydr0xymethyl-Oxetane' A.mixture of- 1,1,1-trimethylolpropane (1340 g2, 10 moles), diethyl carbonate (1298 g., 11 moles), and potassiumhydroxide. (0.5 g.)' dissolved in ethanol (25 ml.) was heated in a glass reaction vessel under a packed 5 3,074.,sea

inchcolumn having a total-reflux head fitted with a condenser for 8 /2 hours, the pot temperature increasing from 72 C. after the first hour up to 150 C. at the end of the period, ethanol being distilled and withdrawn. The pressure was then reduced to 45 mm. Hg to keep the pot temperature below about 210 C. and CO and distillate were evolved. V

The colorless distillate weighed 1060 g. Redistillation of the product gave 1005 g. (86.5%), of a colorless, wafer-soluble liquid, B.P. 85 C. (3 inm.), 11 1.4510.

Analysis.-Calcd. for G l-1 Oxetane oxygen, 13.78%. Found: Oxetane oxygen, 13.78%.

EXAMPLE B Preparation of 3-Mefltyl-3-Hydroxymethyl-Oxezane The procedure of Example A was repeated replacing the trimethylolpropane with 1200 g. (10 moles) of trimethylolethane. The product had a boiling point of 60-l C. at 1 mm. Hg and 11 1.4446.

Analysis.Calcd. for (3 1-1 0 Oxetane oxygen, 15.7%.- Found: Oxetane oxygen, 15.5%.

In the same manner, the 3-hydroxymethyl-oxetanes, in which R" is a higher alkyl having up to 8 carbon atoms, may be made from the compounds RC(CH OH) such as 1,1,l-trimethylolbutane and those described in]. Am. Chem. Soc. 76, 1697 (1954). The simplest 3-hydroxymethyl-oxetane in which R" is H is prepared by the procedure of Example A using HC(CH OH) described by Searles and Throckmorton, Abstracts, Southwest Regional Meeting, American Chemical Society, December 5, 1957.

EXAMPLE C 3- (H ya'roxyeth oxyeth oxym ethyl -3 -M ethyl-Oxetane CH2 CH (EH20 OligOHrO CHzOHzOH A solution of 9.2 g. of sodium in 159 g. of diethylene glycol was prepared by heating at 90 C., after which 48.2 g. of 3-methyl-3-chloromethyloxetane (British Patent 758,450 and J. Applied Chem. 8, 186 (1958), was added dropwise at 90 C. Heating and stirring were continued for 4 hours. The brown slurry was filtered to remove salt and other solids. The filtrate, after neutralization with 8 g. of 36% hydrochloric acid, was again filtered to give a clear red filtrate. Distillation gave 114 g. of recovered glycol and an intermediate cut of 17 g., B.P. 82- 87 C. (0.1 mm), followed by a crude product fraction (34 g.) collected at 89l03 C. (0.1 mm). Redistillation of 27 g. of the crude product through a spinning band column gave 19.5 g. of the pure, colorless oil, B.P. 14014l C. (5 min), 11 1.4527. The product was completely soluble in water. its infra-red spectrum was in agreement with the assigned structure.

Analysis.-Calcd. for (3 1-1 0 Carbon, 56.82%; Hydrogen, 9.54%. Found: Carbon, 56.79%; Hydrogen, 9.58%.

In the following examples, which are illustrative of the invention, the parts and percentages given are by weight unless otherwise noted. The chlorination test method referred to in the examples follows the A.A.T.C.C. (69- 1952) procedure in general except the temperature of chlorination and that of ironing indicated hereinafter. The actual procedure used involves the treatment with a hypochlorite solution containing 0.25% available chlorine at a temperature of 140 F.i2 F. for minutes with intermittent stirring. The treatment is followed by rinses in six fresh water baths at 70 to 80 F. with a squeeze between rinses and drying in air at room temperature. The drying is followed by conditioning for at least four hours at 70 F. and 65% relative humidity. The sample is ironed at 400 F. (iron temperature) for 30 seconds. The chlorine damage referred to hereinbelow is the percentage loss in tensile strengthreferred to herein-below and is calculated by the formula where EXAMPLE 1 (a) An aqueous solution is prepared containing 2.5% of 3-methyl-3-hydroxymethyl-oxetane, 5% of dimethylol- N,N'-ethylene-urea, and 0.4% of zinc fluoborate as a catalyst. A white cotton fabric is padded through this solution, dried at 240 F. for 5 minutes and then heated at 340 F. for 5 minutes to cure the resin.

(b) Another piece of the same cotton fabric is treated in the same way except that the oxetane was reduced to 0.5%.

(c) Another piece of the same cotton fabric is treated in the same way except that the oxetane was reduced to zero.

1 After five full Sanforize washes, the fabrics are subjected to the chlorination test above. In all cases, yellowing after ironing is either non-existent or negligible.

The results of testing for crease-proofing and chlorine damageare shown in the following table (wherein the values given for crease-recovery, are the average of the values for warp and filling):

Table I Tensile Chlorine damage Creasestrength Example recovery before oh1o angle, rination Percent Discoloration on degrees test (warp), loss in chlorination and 1 lbs/sq. in. tensile ironing 114 42 10 none. 118 43 10 none. 120 42 86 severe (brown).

Similar results are obtained when the oxetane used is 3-hydroxymethyl-oxetane or 3-chloromethyl-S-hydroxymethyl-oxetane (J. Org. Chem. 21, 997 (1956)).

Similar results are also obtained when the oxetane used is the 3-ethyl-3-hydroXymethyl-oxetane and when the urea derivative is replaced with dimethoxyrnethyl-N,N'-ethyleneurea. 5

7 Similar results are also obtained when the oxetane used is 3,3-di(hydroxyethoxyethoxymethyl)-oxetane obtained as in Example C from 3,3-di(chloromethyl)-oxetane.

EXAMPLE 2 An aqueous solution is prepared containing 1.0% 3- methyl-3-hydroxymethyl-oxetane, 5% or dimethylol- N,N'-trimethylene-urea, and 0.5% of Zinc fiuoborate as a catalyst. A white cotton fabric is padded through this solution, dried at 240 F. for 5 minutes and then heated at 340 F. for 5 minutes to cure the resin.

After 5 full Sanforize washes the fabric is subjected to the chlorination test with negligible discoloration.

Similar results are obtained when the oxetane is replaced by 3-methyl-3-(hydroxyethoxyethoxymethyl)-oxetane (Example C).

EXAMPLE 3 (a) An aqueous solution is prepared containing 0.5% of 3-methyl-3-hydroxymethyl-oxetane, 5% of dirnethylol trimethoxyrnethyl melamine, and 0.5% of zinc fluoborate as a catalyst. Application to white cotton fabric is made by the procedure of Example 1.

(b) Another piece of the same cotton fabric is treated in the same way except the oxetane is omitted. After five full Sanforize washes and subjection to the chlorination test above, the results obtained are those listed in Table II.

zip-eases Tbll'e II BEFORE CHLORI NAT I ON TEST Elmendorf Chlorine damage Creasetear Tensile recov strength strength Example cry average (warp), Discoloraangle, (warp lbs/sq. Percent tion on degrees and Fill) in. loss in ehlrina in-lbs. tensile tion and ironing 3(a) 110 1.4 i 43 2 none. 3(1)) 115 1 .36 41 v yellow.

Similar results are obtained when the oxetaneis replaced by 3 (t-butyl) -3-hydroxyethoxymetliyl-oxetane.

EF CAMPLE 4 (a) An aqueous solution is p'rpared'containin'g 1% of 3-methyl 3-hydroxyinethyl oxetane; 6% of dimethylol-S- ethyl-tetrahydrotriazone-2, and 1.0% of zinc nitrateas a catalyst. Application to white cotton fabric is made by the procedure of Example 1.

(b) Another piece of the same cotton fabric is treated in the same Way except" the ozietaneis omitted. After five full Sanforize washes and subjection to'the chlorination test, the results are as listed in Table III.

Similar results are obtained when the oxetane'is replaced by 3 (ii-octyl) 3- (hydroiiy(ethoxyhrmiethyl) oxetane.

Table III Chlorine Damage Example Percent loss Diseoloration in tensile on Chlorinastrength tion and Iron- 4(a) 6 slight. 4(1)) 15 yellow.

aminoplast condensate selected from the group consisting of condensates of formaldehyde with a compoundselected from the group consisting of N-,N'ethyleneurea, N,-N'-t'rimethyleneur'ea, a tetrahydro-s-triazofie-Z substituted in the 5-position with a group selected from the group consisting of 8-hydroXyet-hyl, fi-hydroX-yp'ropyL and C -C alkyl groups, and a melamine and 5 to 40% by Weight'of an oxetan'e of the'formula in which R is selected from the group consisting of H, CI-I OH; CH Cl, and alkyl groups having 1 to 8 carbon atoms; 11 is an integer having a value of 2 to 3, and x is an integer havinga value of l to 11, preferably 1 to 3.

2. A CGlTl-POSl'fiOH comprising an aqueous dispersion of a mixture of to by Weightofi a water-dispersiblc aminoplast condensate of formaldehydye with N ,N-ethyleneurea and 5 to 40% by weight of an oxetane as defined in claim 1.

3, Acomposition as defined in claim 2 in which the aminoplast is a' water-dispersi-ble dimethylol-N,N-ethyleneurea.

4. A composition as defined in claim 2 in-Which the aminoplast is a dimethoxymethyl-NN'-ethy1eneurea.

5. A'composi-tion comprising an aqueous dispersion of a mixture of 60 to 95% by Weight of a Water-dispersible aminoplast condensate of formaldehyde with melamine and 5 to 40% by Weight of an exetane as defined in claim 1.

6. A compositionas defined in claim 5 in which the aininopiast is a water-dispersible methylated polymethylolmelamine.

7. A composition as defined in claim 5 in which the aminoplast is a dimethylol trimethoxymethylnielamine.

8. A composition as defined in claim 5 in which the aminoplast is a dimethy'lol-5-ethyl+tetrahydro-s-triazone-2. 

1. A COMPOSITION COMPRISING AN AQUEOUS DISPERSION OF MIXTURE OF 60 TO 95% BY WEIGHT OF A WATER-DISPERSABLE AMINOPLAST CONDENSATE SELECTED FROM THE GROUP CONSISTING OF CONDENSATEA OF FORMALDEHYDE WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF N,N''-ETHYLENEUREA, N,N''-TRIMETHYLENEUREA, A TETRAHYDRO-S-TRIAZONE-2 SUBSTITUTED IN THE 5-POSITION WITH A GROUP SELECTED FROM THE GROUP CONSISTING OF $-HYDROXYETHYL, $-HYDROXYPROPYL, AND (C1-C4)ALKYL GROUPS, AND A MELAMINE AND 5 TO 40% BY WEIGHT OF AN OXETANE OF THE FORMULA 